全文获取类型
收费全文 | 698篇 |
免费 | 12篇 |
国内免费 | 1篇 |
专业分类
化学 | 323篇 |
晶体学 | 5篇 |
力学 | 19篇 |
数学 | 56篇 |
物理学 | 308篇 |
出版年
2021年 | 9篇 |
2020年 | 5篇 |
2019年 | 7篇 |
2018年 | 3篇 |
2017年 | 8篇 |
2016年 | 17篇 |
2015年 | 12篇 |
2014年 | 10篇 |
2013年 | 22篇 |
2012年 | 31篇 |
2011年 | 49篇 |
2010年 | 24篇 |
2009年 | 21篇 |
2008年 | 28篇 |
2007年 | 41篇 |
2006年 | 23篇 |
2005年 | 23篇 |
2004年 | 35篇 |
2003年 | 27篇 |
2002年 | 39篇 |
2001年 | 10篇 |
2000年 | 15篇 |
1999年 | 8篇 |
1998年 | 12篇 |
1997年 | 5篇 |
1996年 | 7篇 |
1995年 | 12篇 |
1994年 | 12篇 |
1993年 | 6篇 |
1992年 | 18篇 |
1991年 | 11篇 |
1990年 | 13篇 |
1989年 | 16篇 |
1988年 | 8篇 |
1987年 | 13篇 |
1986年 | 4篇 |
1985年 | 12篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1981年 | 10篇 |
1980年 | 9篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 10篇 |
1974年 | 4篇 |
1973年 | 5篇 |
1969年 | 3篇 |
排序方式: 共有711条查询结果,搜索用时 11 毫秒
81.
Okamura WH Zhu GD Hill DK Thomas RJ Ringe K Borchardt DB Norman AW Mueller LJ 《The Journal of organic chemistry》2002,67(5):1637-1650
Isotope-labeled drug molecules may be useful for probing by NMR spectroscopy the conformation of ligand associated with biological hosts such as membranes and proteins. Triple-labeled [7,9,19-(13)C(3)]-vitamin D(3) (56), its 25-hydroxylated and 1 alpha,25-dihydroxylated metabolites (58 and 68, respectively), and other labeled materials have been synthesized via coupling of [9-(13)C]-Grundmann's ketone 39 or its protected 25-hydroxy derivative 43 with labeled A ring enyne fragments 25 or 26. The labeled CD-ring fragment 39 was prepared by a sequence involving Grignard addition of [(13)C]-methylmagnesium iodide to Grundmann's enone 28, oxidative cleavage, functional group modifications leading to seco-iodide 38, and finally a kinetic enolate S(N)2 cycloalkylation. The C-7,19 double labeling of the A-ring enyne was achieved by the Corey-Fuchs/Wittig processes on keto aldehyde 11. By employing these labeled fragments in the Wilson-Mazur route, the C-7,9,19 triple-(13)C-labeled metabolites 56, 58, and 68 as well as other (13)C-labeled metabolites have been prepared. In an initial NMR investigation of one of the labeled metabolites prepared in this study, namely [7,9,19-(13)C(3)]-25-hydroxyvitamin D(3) (58), the three (13)C-labeled carbons of the otherwise water insoluble steroid could be clearly detected by (13)C NMR analysis at 0.1 mM in a mixture of CD(3)OD/D(2)O (60/40) or in aqueous dimethylcyclodextrin solution and at 2 mM in 20 mM sodium dodecyl sulfate (SDS) aqueous micellar solution. In the SDS micellar solution, a double half-filter NOESY experiment revealed that the distance between the H(19Z) and H(7) protons is significantly shorter than that of the corresponding distance calculated from the solid state (X-ray) structure of the free ligand. The NMR data in micelles reveals that 58 exists essentially completely in the alpha-conformer with the 3 beta-hydroxyl equatorially oriented, just as in the solid state. The shortened distance (H(19Z))-H(7)) in micellar solutions as compared to that in the solid state is most easily rationalized on the basis that the 5(10)-torsion angle in 58 is decreased in micellar solutions as compared to that in the solid state. 相似文献
82.
83.
Singh J Kronenthal DR Schwinden M Godfrey JD Fox R Vawter EJ Zhang B Kissick TP Patel B Mneimne O Humora M Papaioannou CG Szymanski W Wong MK Chen CK Heikes JE DiMarco JD Qiu J Deshpande RP Gougoutas JZ Mueller RH 《Organic letters》2003,5(17):3155-3158
[reaction: see text] An efficient asymmetric synthesis of the vasopeptidase inhibitor BMS-189921 was accomplished. Two short enantioselective syntheses of the common key intermediate (S)-alpha-aminoazepinone 6b were developed. Olefin 3 was converted to 6b via asymmetric hydrogenation. Alternatively, enyne 12 was converted to racemic alpha-aminoazepinone 15b, which was transformed to 6b by a practical dynamic resolution. 相似文献
84.
Taw FL Mueller AH Bergman RG Brookhart M 《Journal of the American Chemical Society》2003,125(32):9808-9813
Cationic Rh(III) complex [Cp(PMe(3))Rh(SiPh(3))(CH(2)Cl(2))]BAr(4)' (1) activates the carbon-carbon bond of aryl and alkyl cyanides (R-CN, where R = Ph, (4-(CF(3))C(6)H(4)), (4-(OMe)C(6)H(4)), Me, (i)Pr, (t)Bu) to produce complexes of the general formula [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. With the exception of the (t)BuCN case, every reaction proceeds at room temperature (t(1/2) < 1 h for aryl cyanides, t(1/2) < 14 h for alkyl cyanides). A general mechanism is presented on the basis of (1) an X-ray crystal structure determination of an intermediate isolated from the reaction involving 4-methoxybenzonitrile and (2) kinetic studies performed on the C-C bond cleavage of para-substituted aryl cyanides. Initial formation of an eta(1)-nitrile species is observed, followed by conversion to an eta(2)-iminoacyl intermediate, which was observed to undergo migration of R (aryl or alkyl) to rhodium to form the product [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. 相似文献
85.
Larissa Mueller Heike Traub Norbert Jakubowski Daniela Drescher Vladimir I. Baranov Janina Kneipp 《Analytical and bioanalytical chemistry》2014,406(27):6963-6977
The analysis of single cells is a growing research field in many disciplines such as toxicology, medical diagnosis, drug and cancer research or metallomics, and different methods based on microscopic, mass spectrometric, and spectroscopic techniques are under investigation. This review focuses on the most recent trends in which inductively coupled plasma mass spectrometry (ICP-MS) and ICP optical emission spectrometry (ICP-OES) are applied for single-cell analysis using metal atoms being intrinsically present in cells, taken up by cells (e.g., nanoparticles), or which are artificially bound to a cell. For the latter, especially element tagged antibodies are of high interest and are discussed in the review. The application of different sample introduction systems for liquid analysis (pneumatic nebulization, droplet generation) and elemental imaging by laser ablation ICP-MS (LA-ICP-MS) of single cells are highlighted. Because of the high complexity of biological systems and for a better understanding of processes and dynamics of biologically or medically relevant cells, the authors discuss the idea of “multimodal spectroscopies.” 相似文献
86.
87.
Synthesis and physical properties of highly branched perfluorinated polymers from AB and AB2 monomers 下载免费PDF全文
Matthew J. Quast Aaron D. Argall Cassandra J. Hager Anja Mueller 《Journal of polymer science. Part A, Polymer chemistry》2015,53(16):1880-1894
Highly branched perfluorinated aromatic polyether copolymers were prepared from the polycondensation of the AB2 monomer, 3,5‐bis[(pentafluorobenzyl)oxy]benzyl alcohol with a variety of fluoroaryl and alkyl bromide AB comonomers. The structures and comonomer distribution of the resulting polymers were characterized in detail. 1H NMR data from kinetic trials illustrated that perfluoroaryl AB comonomer distribution correlated to AB comonomer sterics. 19F NMR data revealed that fluorinated AB monomers and 3‐bromo‐1‐propanol AB monomers were distributed within the AB2 polymer backbone, while longer alkyl bromide AB monomers, 6‐bromo‐1‐hexanol, were mostly distributed along hyperbranched polymer chain ends. In general, as AB comonomer incorporation increased for nonsterically hindered copolymers, thermal decomposition onset increased and glass transition temperatures decreased. The combined data demonstrated the effect of comonomer distribution and sterics on physical properties of AB2‐based polymer systems. The resulting materials were used to cast thin polymer films for measurement of contact angle, which were shown to be directly related to comonomer content. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1880–1894 相似文献
88.
Valerie Derpmann David Mueller Iustinian Bejan Hannah Sonderfeld Sonja Wilberscheid Ralf Koppmann Klaus J. Brockmann Thorsten Benter 《Journal of the American Society for Mass Spectrometry》2014,25(3):329-342
We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O2 – or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O2 – leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry. Figure
? 相似文献
89.
Tao Wang Dr. Yuzhou Wu Dr. Seah Ling Kuan Oliver Dumele Dr. Markus Lamla Dr. David Y. W. Ng Matthias Arzt Jessica Thomas Jan O. Mueller Prof. Dr. Christopher Barner‐Kowollik Prof. Dr. Tanja Weil 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):228-238
A disulfide intercalator toolbox was developed for site‐specific attachment of a broad variety of functional groups to proteins or peptides under mild, physiological conditions. The peptide hormone somatostatin (SST) served as model compound for intercalation into the available disulfide functionalization schemes starting from the intercalator or the reactive SST precursor before or after bioconjugation. A tetrazole–SST derivative was obtained that undergoes photoinduced cycloaddition in mammalian cells, which was monitored by live‐cell imaging. 相似文献
90.
Alshymaa Abdel-Rahman Gomaa Usama Ramadan Abdelmohsen Markus Krischke Martin J. Mueller Amira Samir Wanas 《Natural product research》2020,34(18):2612-2615
AbstractThe present study evaluates the chemical composition of Zinnia elegans and Gazania rigens based on their metabolomic profiles using liquid chromatography coupled with high-resolution mass spectrometry (LC‐HR-MS), alongside with the anti-infective activities of their ethanol extracts, as well as, different fractions. A significant difference was observed between the LC-MS profiles of the two plants such as, coumarins, sesquiterpene lactones and phenylethanoids which were characteristic for Z. elegans, while amides and phenolic acid derivatives were characteristic for G. rigens. These results highlight the chemical potential of Z. elegans and G. rigens. Furthermore, the ethyl acetate fraction of Z. elegans showed a significant antimalarial activity with IC50 values of 21.03 and 13.72?µg/mL against Plasmodium falciparum D6 and P. falciparum W2, respectively. 相似文献